JP5376793B2 - Photocurable resin composition, cured product pattern thereof, and printed wiring board comprising the cured product pattern - Google Patents

Abstract

The invention provides an alkali developing type light-cured resin composition and a cured resin pattern and a printed board. The composition has high sensitivity for active energy ray, an exposure curability directly depicted by laser, and a developing ability, a finger touch dryness, a solder thermal endurance, a chemical gold plating resistance, an alkali tolerance, and a PCT and PCBT resistance are excellent, thus the composition can be used as a solder resist. The alkali developing type light-cured resin composition comprises: (A) a carboxylic acid-containing photosensitive resin shown as a general formula (I), (B) a photopolymerization initator, (C) a compound with more than two olefinic unsaturated groups in one molecule, in the general formula (I), R<1> is a hydrogen atom or a methyl, R<2> is a straight-chain, branched chain or cyclic alkyl with 2-6 carbon atoms, and R<3> is hydrogen atom or carboxylic acid ester residue.

Description

  The present invention relates to an alkali-developable photocurable resin composition that is excellent in sensitivity to active energy rays and is useful as a solder resist.

Recently, laser scanning exposure has become widespread as an exposure means for printed wiring board solder resist from the viewpoint of excellent alignment accuracy. In laser exposure, an image is formed while scanning a solder resist on a patterned wiring board without using a photomask, but a conventional solder resist has an appropriate exposure amount of 200 mJ / cm ² or more. There is a drawback that it takes a very long time for exposure, and a solder resist corresponding to laser exposure is required to have very high sensitivity.

  From such a background, a photosensitive composition capable of exhibiting high photopolymerization ability has been proposed (see, for example, Patent Document 1 and Patent Document 2). However, some of the photosensitive compositions that have been proposed so far can certainly exhibit high photopolymerization ability, but the sensitivity is not necessarily sufficient for laser direct exposure. In addition, the properties other than the sensitivity required for the photosensitive composition are not necessarily sufficient. Specifically, in the composition disclosed in Patent Document 1, only glycidyl methacrylate is exemplified as a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule used for forming a carboxyl group-containing photosensitive resin. However, not only is the sensitivity insufficient, but there is a tendency for the developability to deteriorate when the added amount is increased. On the other hand, when using caprolactone-modified acrylate, which is proposed in Patent Document 2 and chain-reacted with ε-caprolactone and molecularly extended, the sensitivity is high, but the dryness to touch is extremely poor, and the solder heat resistance is high. Sex was also insufficient.

Furthermore, the alkali development type photo solder resist still has problems in terms of durability. That is, the alkali developing type photo solder resist is inferior in chemical resistance, water resistance, heat resistance and the like as compared with conventional thermosetting type and solvent developing type. This is due to the fact that the alkali development type photo solder resist mainly contains a hydrophilic group in order to enable alkali development. Thereby, a chemical | medical solution, water, water vapor | steam etc. are easy to osmose | permeate, a chemical-resistant fall and the adhesiveness of a resist film and copper are reduced. As a result, alkali resistance as chemical resistance is weak, and especially in semiconductor packages such as BGA and CSP, PCT resistance (pressure cooker resistance) that should be called moisture heat resistance is necessary, but under such severe conditions Is currently only a few hours to a few dozen hours. In most cases, in the PCBT test in which a voltage is applied under the PCT condition, defects due to the occurrence of migration are confirmed within a few hours.
JP 2007-41502 (Claims) JP 2007-3590 A (Claims)

  The present invention has been developed in view of the above-mentioned problems, is highly sensitive to active energy rays, has excellent exposure curability by direct drawing, and developability, touch drying property, solder heat resistance. It is an object of the present invention to provide an alkali development type photo-curable resin composition that is excellent in resistance, electroless gold plating property, alkali resistance, PCT and PCBT resistance, and is useful as a solder resist.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have used a photocurable resin composition comprising a carboxylic acid-containing photosensitive resin containing a specific structure as a photosensitive resin and combining this with other components. The inventors have found that the above problems can be solved and have completed the present invention.

That is, the present invention relates to (A) a carboxylic acid-containing photosensitive resin containing a structure represented by the general formula (I), (B) a photopolymerization initiator, and (C) two or more ethylenic groups in one molecule. An alkali-developable photocurable resin composition comprising a compound having a saturated group:

In general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R ³ represents a hydrogen atom or an organic acid ester residue. .

Here, R ³ in the general formula (I) may be an acid anhydride residue or a (meth) acrylic acid residue in one embodiment.

The (B) photopolymerization initiator includes an oxime ester photopolymerization initiator including a structure represented by the general formula (II) and an aminoacetophenone photopolymerization initiator including a structure represented by the general formula (III). And one or a mixture of two or more selected from the group consisting of acylphosphine oxide photopolymerization initiators containing a structure represented by the general formula (IV):

In General Formulas (II) to (IV), R ¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), or 1 to 20 carbon atoms. A linear, branched or cyclic alkyl group (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), 5 to 5 carbon atoms An cycloalkyl group having 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one Which may be substituted with the above hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or Represents a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ³ and R ⁴ each independently represents a linear, branched or cyclic alkyl group or arylalkyl group having 1 to 12 carbon atoms,
R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ are bonded to form a cyclic alkyl ether group. You may,
R ⁷ and R ⁸ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (halogen atom, alkyl group, or alkoxy group). Or an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms). However, the case where both R ⁷ and R ⁸ are R—C (═O) — groups is excluded.

Further, the resin composition of the present invention may further contain (D) a thermosetting component.
The resin composition of the present invention may be a solder resist further containing (E) a colorant.

  In another aspect, the present invention is a photocurable dry film obtained by applying the photocurable resin composition of the present invention to a carrier film and drying it.

  In another aspect, the present invention is a cured product pattern formed using a resin layer comprising the photocurable resin composition, wherein the pattern formation is performed by irradiation with active energy rays. It is a thing putter. Here, the pattern formation by active energy ray irradiation may be by direct drawing using active energy rays having a wavelength of 350 nm to 410 nm.

  Moreover, this invention is a printed wiring board which comprises the said hardened | cured material pattern on a copper layer in another aspect.

  In this specification, (meth) acrylic acid is used as a term representing acrylic acid and / or methacrylic acid, and the same applies to other similar expressions.

Hereinafter, each component of the photocurable resin composition of the present invention will be described in detail.
The carboxylic acid-containing photosensitive resin (A) contained in the photocurable resin composition of the present invention includes a structure represented by the general formula (I), and further contains a carboxylic acid in the molecule.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R ³ represents a hydrogen atom or an organic acid ester residue.
Here, the organic acid ester residue represented by R ³ includes an acid anhydride residue or a (meth) acrylic acid residue, and specific examples of the acid anhydride residue will be described later (b And unsaturated group-containing acid anhydrides and (d) polybasic acid anhydrides.

  The carboxylic acid-containing photosensitive resin (A) of the present invention comprises (a) a compound having at least two hydroxyl groups and one carboxyl group in one molecule, (b) an unsaturated group-containing acid anhydride, (c) Although it can be obtained according to the following procedures (1) to (3) using an epoxy compound having at least two epoxy groups in one molecule and (d) a polybasic acid anhydride, it is not limited thereto. It is not something.

That is,
(1) An unsaturated group-containing acid anhydride (b) is reacted with a compound (a) having at least two hydroxyl groups and one carboxyl group in one molecule, and two (meth) in one molecule. A compound having an acrylic group and one carboxyl group is synthesized. It can be obtained by reacting the resulting compound with an epoxy compound (c) having at least two epoxy groups in one molecule and further reacting with a polybasic acid anhydride (d).

  A feature of the system (1) is that it is effective for increasing the sensitivity by increasing the concentration of the photosensitive group. Although details are not clear, improvement in developability was also confirmed. This is presumably because the emulsion effect was enhanced by increasing the affinity with other components not containing a carboxyl group as the acrylic group concentration in the resin increased. Furthermore, it was confirmed that the alkali resistance accompanying the increase in the crosslinking density and the PCT and PCBT resistances accompanying the improvement in hydrophobicity were improved.

  (2) An unsaturated group-containing acid anhydride (b) is reacted with a compound (a) having at least two hydroxyl groups and one carboxyl group in one molecule, and two (meth) in one molecule. A compound having an acrylic group and one carboxyl group is synthesized. The resulting compound is reacted with an epoxy compound (c) having at least two epoxy groups in one molecule. The compound obtained can be obtained by further reacting a compound (a) having at least two hydroxyl groups and one carboxyl group in one molecule, and further reacting with a polybasic acid anhydride.

  The feature of the system (2) is that, as in (1), it is effective in increasing the sensitivity by increasing the concentration of the photosensitive group. Further, as a further feature of the system (2), the photosensitive unit (acrylic group) and the developing unit (carboxyl group) are completely separate. With this effect, it was confirmed that the maximum development life was extended from (1) while maintaining the same sensitivity as (1). Moreover, the improvement of developability and the improvement of PCT and PCBT tolerance were also confirmed similarly to (1).

  (3) The epoxy compound (c) having at least two epoxy groups in one molecule is reacted with the compound (a) having at least two hydroxyl groups and one carboxyl group in one molecule. It is obtained by reacting the unsaturated group-containing acid anhydride (b) with the resulting compound and then further reacting with a polybasic acid anhydride (d).

  As a feature of the system (3), as in (1) and (2), it is effective to increase the sensitivity by increasing the concentration of the photosensitive group. As for (3), as in (1) and (2), improvement in developability was also confirmed. However, unlike (2), the photosensitive unit (acrylic group) and the developing unit (carboxyl group) become random, and as a result, it tends to be difficult to completely control the resin structure.

  Each of these systems (1) to (3) has excellent characteristics, but (2) or (1) is particularly preferable from the viewpoint of the balance between photosensitivity and developability and the properties of the obtained cured product. it is conceivable that.

  Specific examples of (a) compounds having at least two hydroxyl groups and one carboxyl group in one molecule, which are used for the synthesis of (A) a carboxylic acid-containing photosensitive resin described in (1) to (3) above. Examples thereof include polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid. Particularly preferable examples include dimethylolpropionic acid.

  (B) As an unsaturated group containing acid anhydride, an acrylic acid anhydride and a methacrylic acid anhydride are mentioned, These can be used individually or in combination of 2 or more types.

  (C) Examples of the epoxy compound having at least two epoxy groups in one molecule include various known and commonly used epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and brominated bisphenol A. Type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin, bisphenol A novolak type epoxy resin Glycidyl ether compounds such as terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and dimer acid diglycidyl ester; Glycidylamine compounds such as ricidyl isocyanurate, N, N, N ′, N′-tetraglycidylmetaxylenediamine, N, N, N ′, N′-tetraglycidylbisaminomethylcyclohexane, N, N-diglycidylaniline Is used. Among these, a phenol novolac type epoxy resin and a cresol novolac type epoxy resin are preferable because they can provide a cured coating film having high sensitivity and excellent heat resistance. Furthermore, a cresol novolac type epoxy resin having a softening point of 60 ° C. or higher is more preferable because it is excellent in dryness to touch. These polyfunctional epoxy compounds can be used alone or in combination of two or more.

  (D) Polybasic acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride An acid, trimellitic anhydride, pyromellitic anhydride, etc. are mentioned, These can be used individually or in combination of 2 or more types.

  In addition, the carboxylic acid-containing photosensitive resin (A) obtained in (1) to (3) is further reacted with (e) a compound having both a cyclic ether group and an ethylenically unsaturated group in one molecule. The obtained resin may be used.

  Examples of the compound (e) having both a cyclic ether group and an ethylenically unsaturated group in one molecule include 2-hydroxyethyl (meth) acrylate glycidyl ether, 2-hydroxypropyl (meth) acrylate glycidyl ether, 3-hydroxypropyl ( (Meth) acrylate glycidyl ether, 2-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, 2-hydroxypentyl (meth) acrylate glycidyl ether, 6-hydroxyhexyl (meth) acrylate glycidyl ether or Examples include epoxy group-containing ethylenically unsaturated monomers such as glycidyl (meth) acrylate, and these can be used alone or in combination of two or more. Among such epoxy group-containing ethylenically unsaturated monomers, 4-hydroxybutyl (meth) acrylate glycidyl ether and glycidyl (meth) acrylate are particularly preferable because they have moderate productivity and photocurability.

  The addition amount of the compound (e) having both a cyclic ether group and an ethylenically unsaturated group in one molecule is preferably 5% equivalent to 40% equivalent, more preferably equivalent to the acid anhydride residue. 10% equivalent to 30% equivalent. An addition amount of 5% equivalent or more is preferable from the viewpoint of increasing sensitivity and improving electroless gold plating resistance. On the other hand, if it exceeds 40% equivalent, the maximum development life may be shortened or the dryness to touch may be deteriorated. It is not preferable. Modification by these compounds (e) was confirmed to have a synergistic effect on further sensitivity enhancement by improving the crosslinking density, alkali resistance, PCT and PCBT resistance.

  The acid value of the carboxyl group-containing resin (A) is preferably in the range of 40 to 200 mgKOH / g, more preferably in the range of 80 to 120 mgKOH / g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed area by the developer proceeds and the line becomes thinner than necessary. Depending on the case, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group containing resin (A) changes with resin frame | skeleton, generally what is in the range of 2000-50000, Furthermore, 5000-20000 is preferable. If the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 50,000, the developability may be remarkably deteriorated, and the storage stability may be inferior.

  The blending ratio of such a carboxyl group-containing resin (A) is preferably 20 to 60% by mass and more preferably 30 to 50% by mass with respect to the total mass of the resin composition. When the amount is less than the above range, the coating film strength may decrease, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity may increase or the resist coating property may decrease, which is not preferable.

  In the present invention, in addition to the carboxylic acid-containing photosensitive resin (A), a known and commonly used carboxylic acid resin, particularly preferably a photosensitive carboxylic acid resin, can be added.

Next, the photopolymerization initiator (B) will be described.
As the photopolymerization initiator (B), an oxime ester photopolymerization initiator (B-1) containing a structure represented by the following general formula (II), an α containing a structure represented by the following general formula (III) -1 type selected from the group which consists of an amino acetophenone type photoinitiator (B-2) and the acyl phosphine oxide type photoinitiator (B-3) containing the structure represented by following formula (IV), Or it is preferable to use 2 or more types of photoinitiators.

In general formulas (II) to (IV),
R ¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. A group (which may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, or 2 to 20 carbon atoms Alkanoyl group or benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one Which may be substituted with the above hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or Represents a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ³ and R ⁴ each independently represents a linear, branched or cyclic alkyl group or arylalkyl group having 1 to 12 carbon atoms,
R ⁵ and R ⁶ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ are bonded to form a cyclic alkyl ether group. Well,
R ⁷ and R ⁸ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (halogen atom, alkyl group, or alkoxy group). Or an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms). However, the case where both R ⁷ and R ⁸ are R—C (═O) — groups is excluded.

The oxime ester photopolymerization initiator (B-1) having a group represented by the general formula (II) is preferably 2- (acetyloxyiminomethyl) thioxanthene represented by the following formula (V). -9-On:

Compounds represented by the following general formula (VI):

(Where
R ⁹ is a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, or an alkanoyl group having 2 to 12 carbon atoms. Group, an alkoxycarbonyl group having 2 to 12 carbon atoms (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and 1 in the middle of the alkyl chain) Which may have more than one oxygen atom), or a phenoxycarbonyl group,
R ¹⁰ and R ¹² are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear or branched chain having 1 to 20 carbon atoms, or A cyclic alkyl group (which may be substituted with one or more hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, a carbon number Represents an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ¹¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. (It may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), a C5-C8 cycloalkyl group, a C2-C20 An alkanoyl group or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group) is represented. And a compound represented by the following general formula (VII):

(Where
R ¹³ , R ¹⁴ and R ¹⁹ each independently represent a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms,
R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms,
M represents O, S or NH;
m and n each independently represents an integer of 0 to 5. )
Is mentioned.

  Among these, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by formula (V) and a compound represented by formula (VI) are more preferable. Examples of commercially available products include CGI-325, Irgacure OXE01, and Irgacure OXE02 manufactured by Ciba Specialty Chemicals. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  As the α-aminoacetophenone photopolymerization initiator (B-2) having a structure represented by the general formula (III), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Specialty Chemicals.

  Examples of the acylphosphine oxide photopolymerization initiator (B-3) having a structure represented by the general formula (IV) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl). ) -Phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

  The blending ratio of such a photopolymerization initiator (B) is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 15 parts with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). It can be selected from the range of parts by mass. If it is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating film properties such as chemical resistance are deteriorated. On the other hand, if it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (B) becomes violent and the deep curability tends to decrease, which is not preferable.

  In the case of the oxime ester photopolymerization initiator including the structure represented by the formula (II), the blending amount is preferably 0.01 to 100 parts by mass of the carboxylic acid-containing resin (A). It is desirable to select from 20 parts by mass, more preferably from 0.01 to 5 parts by mass.

  In the composition of the present invention, photopolymerization initiators other than the above-mentioned compounds, photopolymerization initiation assistants, and sensitizers can be used, for example, benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketals. Examples thereof include compounds, benzophenone compounds, xanthone compounds, and tertiary amine compounds.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.
Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

  Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4,4′-diethylamino. Dialkylamino benzophenone such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -Butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

  Of the above, thioxanthone compounds and tertiary amine compounds are preferred. The inclusion of a thioxanthone compound is preferable from the viewpoint of deep curable properties, and among these, thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone are preferable.

  The mixing ratio of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). If the mixing ratio of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition. A colored solder resist film reflecting the color can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  As a compounding ratio of such a tertiary amine compound, the ratio of 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the carboxylic acid-containing resin (A). It is. When the mixing ratio of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. When the amount exceeds 20 parts by mass, light absorption on the surface of the dried solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

  These photopolymerization initiators, photopolymerization initiation assistants, and sensitizers can be used alone or as a mixture of two or more.

  The total amount of such photopolymerization initiator (B), photopolymerization initiation assistant, and sensitizer may be in a range of 35 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing resin (A). preferable. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  Next, the compound (C) having two or more ethylenically unsaturated groups in the molecule will be described.

  The compound (C) having two or more ethylenically unsaturated groups in the molecule used in the photocurable resin composition of the present invention is photocured by irradiation with active energy rays and contains the ethylenically unsaturated groups. The carboxylic acid-containing photosensitive resin (A) is insolubilized or assists insolubilization in an alkaline aqueous solution. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding ratio of the compound (C) having two or more ethylenically unsaturated groups in the molecule is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). The ratio is more preferably 5 to 70 parts by mass. When the blending ratio is less than 1 part by mass, the photocurability is lowered, and pattern formation by alkali development after irradiation with active energy rays becomes difficult, which is not preferable. On the other hand, when it exceeds 100 mass parts, since the solubility with respect to aqueous alkali solution falls and a coating film tends to become weak, it is unpreferable.

Next, the thermosetting component (D) will be described.
A thermosetting component (D) can be added to the photocurable resin composition of the present invention in order to impart heat resistance. Particularly preferred is a thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  Examples of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule include any of 3, 4, or 5-membered cyclic ether groups or cyclic thioether groups in the molecule. Examples thereof include compounds having two or more of one or two kinds of groups. For example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound (D-1), at least in the molecule. Examples thereof include a compound having two or more oxetanyl groups, that is, a polyfunctional oxetane compound (D-2), a compound having two or more cyclic thioether groups in the molecule, that is, an episulfide compound (D-3).

  Examples of the polyfunctional epoxy compound (D-1) include, for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epicron 840, Epicron 850, Epicron 1050, manufactured by Dainippon Ink & Chemicals, Inc. Epicron 2055, Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Toto Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo Co., Ltd. A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); Epicoat YL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Epototo YDB-400, YDB- manufactured by Tohto Kasei Co., Ltd. 500, D.C. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (all trade names); Epicoat 152 and Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, Epicoat 807 manufactured by Japan Epoxy Resin, Epototo YDF-170 manufactured by Toto Kasei Co., YDF -175, YDF-2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Specialty Chemicals (all are trade names); Epotot ST-2004, ST-2007, ST-3000 manufactured by Tohto Kasei Hydrogenated bisphenol A type epoxy resin such as EPOCOAT 604 manufactured by Japan Epoxy Resin Co., Ltd., Epotot YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumitomo Chemical Industries Epoxy ELM-120 etc. All are trade names) glycidylamine type epoxy resin; Hydantoin type epoxy resins such as Araldide CY-350 (trade name) manufactured by Ciba Specialty Chemicals; Celoxide 2021 manufactured by Daicel Chemical Industries, Ciba Specialty Chemicals Alicyclic epoxy resins such as Araldide CY175, CY179, etc. (both trade names) manufactured by YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Bisphenol A novolac type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan Epoxy Resin; Epicoat YL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. Name) Tetraphenylolethane type Poxy resin; Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (both are trade names); Diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Nippon Steel; ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene groups such as HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; Epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nippon Oil &Fats; In addition, cyclohexylmaleimide and glycidyl Methacrylate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.), etc. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  Examples of the polyfunctional oxetane compound (D-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane Alcohol and novolak resin, poly (p-hydroxystyrene), cardo type Scan phenols, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the episulfide compound (D-3) include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resin Co., Ltd. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The blending ratio of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is preferably 0 with respect to 1 equivalent of the carboxyl group of the carboxylic acid-containing photosensitive resin (A). .6 to 2.5 equivalents, and more preferably 0.8 to 2.0 equivalents. When the blending amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is less than 0.6 equivalent, it causes a carboxyl group to remain in the solder resist film. Since heat resistance, alkali resistance, electrical insulation, etc. will fall, it is not preferable. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film may decrease.

  When using a thermosetting component (D) for the photocurable resin composition of this invention, it is preferable to use a thermosetting catalyst together. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and those that are commercially available ,example 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT3503N, U-CAT3502T (all dimethylamine block isocyanate compounds manufactured by San Apro) Product names), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The blending ratio of these thermosetting catalysts is sufficient at a normal quantitative ratio, and for example, preferably 0.1 to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A) or thermosetting component (D). It is 20 mass parts, More preferably, it is 0.5-15.0 mass parts.

Next, the colorant (E) that can be used in the photocurable resin composition of the present invention will be described.
A coloring agent can be mix | blended with the photocurable resin composition of this invention. As the colorant, conventionally known colorants such as red, blue, green, yellow and black can be used, and any of pigments, dyes and dyes may be used. However, it is preferable not to contain a halogen and an azo compound from the viewpoint of reducing environmental burden and affecting the human body.

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds classified as Pigment, specifically, the following color index (CI; The Society of Dyers and Colorists) (Issued by The Society of Dyers and Colorists) can be listed with numbers: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4 , Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

  The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, as the green colorant, there are phthalocyanine type and anthraquinone type, and specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. can be used. . In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.

  Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

  Isoindolinone type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

  Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

  Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

  Monoazo: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116 , 167, 168, 169, 182, 183.

  Disazo: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.

  Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

  Disazo: Pigment Red 37, 38, 41.

  Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.

  Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

  Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

  Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

  Condensed azo series: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221 and Pigment Red 242.

  Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.
In addition, colorants such as purple, orange, brown, and black may be added for the purpose of adjusting the color tone.

  Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Rack 1, there is a C.I. Pigment Black 7 and the like.

  Although the specific blending ratio of the colorant is influenced by the type of the colorant used and the type of other additives, it cannot be generally stated, but the carboxylic acid-containing photosensitivity of the photosensitive resin composition of the present invention. It is preferable to mix 0 to 5 parts by mass with respect to 100 parts by mass of the resin. Particularly preferable colorants that can be used in an amount of 0.05 to 3 parts by weight are blue and green phthalocyanine, anthraquinone, yellow anthraquinone, red diketopyrrolopyrrole, anthraquinone, And it does not contain a halogen atom. Further, pigment-based blue and green are preferable from the viewpoint of heat resistance, and dye-based blue, green, and red colorants are preferable from the viewpoint of sensitivity and resolution.

  The photocurable resin composition of the present invention can be blended with a filler as necessary in order to increase the physical strength of the coating film. As such a filler, publicly known and commonly used inorganic or organic fillers can be used, and barium sulfate, spherical silica and talc are particularly preferably used. Furthermore, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733 manufactured by Hanse-Chemie, in which nano silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin (D-1), XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product grade names) and NANOOX (trade name) XP 0516, XP 0525, XP 0314 (all product grades) manufactured by Hanse-Chemie Name) etc. can also be used. These may be used alone or in combination of two or more.

  The blending ratio of these fillers is preferably 300 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the carboxylic acid-containing photosensitive resin (A). 150 parts by mass. When the blending ratio of the filler exceeds 300 parts by mass, the viscosity of the photosensitive composition is increased, the printability may be lowered, and the cured product may be brittle, which is not preferable.

  Further, the photocurable resin composition of the present invention is an organic solvent for the synthesis of the carboxylic acid-containing photosensitive resin (A) and for the preparation of the composition, or for adjusting the viscosity for application to a substrate or carrier film. Can be used.

  Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  The photocurable resin composition of the present invention may further include, as necessary, known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, and phenothiazine, finely divided silica, organic bentonite, and montmorillonite. Known and commonly used thickeners, silicone-based, fluorine-based and polymer-based antifoaming agents and / or leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, antioxidants, rust inhibitors, etc. The known and conventional additives such as can be blended.

  The photocurable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method. After coating by a curtain coating method or the like, a tack-free coating film is formed by volatile drying (temporary drying) of an organic solvent contained in the composition at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the resin composition of this invention on a carrier film, making it dry and making a dry film, and laminating | stacking what wound up this on a base material.

  The coating film obtained as described above, or the resin layer on the carrier film (along with the “coating film”, these are referred to as “resin layer”) is exposed by irradiation with active energy rays, and an exposed portion (active The portion irradiated by the energy rays is cured.

  Specifically, by a contact type (or non-contact type), pattern exposure is performed by selective exposure using an active energy ray or direct drawing of an active energy ray using a laser direct exposure machine through a photomask on which a pattern is formed. The exposed portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3% sodium carbonate aqueous solution) to form a resist pattern. Furthermore, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxylic acid-containing resin (A) and two or more cyclic ether groups and / or cyclic thioether groups in the molecule are obtained. The thermosetting component which it has reacts and can form the cured coating film excellent in various characteristics, such as heat resistance, chemical resistance, moisture absorption resistance, adhesiveness, and an electrical property.

  High frequency circuit using paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine / polyethylene / PPO / cyanate ester, etc. Examples include materials such as copper clad laminates, and copper graded laminates of all grades (FR-4, etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates and the like.

  The volatile drying performed after the application of the photocurable resin composition of the present invention includes a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. And a method of spraying the hot air against the support from a nozzle).

As an exposure apparatus used for the active energy ray irradiation, an ultraviolet irradiation apparatus and a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can be used. As the active energy ray, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. Further, the exposure amount varies depending the thickness or the like, typically 5 to 200 mJ / cm ^2, preferably from 5 to 100 mJ / cm ^2, more preferably be in the range of 5~50mJ / cm ^2. As the direct drawing device, for example, those manufactured by Nippon Orbotech, Pentax, etc. can be used, and any device may be used as long as it oscillates laser light having a maximum wavelength of 350 to 410 nm. .

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of carboxylic acid-containing photosensitive resin (A)>
Resin synthesis example 1 (A-1)
600 g of diethylene glycol monoethyl ether acetate, 442.2 parts (3.3 mol) of dimethylolpropionic acid, 1031.8 parts (6.7 mol) of methacrylic anhydride, 3.0 parts of methylhydroquinone, 8.5 parts of triphenylphosphine Part was added and reacted at 95 ° C. for 8 hours. Next, 800 g of diethylene glycol monoethyl ether acetate, orthocresol novolak type epoxy resin [manufactured by Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 2140 g (number of glycidyl groups ( The total number of aromatic rings): 10.0 mol), 3.0 parts of methylhydroquinone and 1000 parts of carbitol acetate were charged and heated to 90 ° C. with stirring to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., 10.0 parts of triphenylphosphine was charged, heated to 100 ° C., and reacted for about 30 hours. Next, 912 parts (6.0 mol) of tetrahydrophthalic anhydride was added thereto, heated to 95 ° C., reacted for about 6 hours, then cooled, and the acid value of the solid component was 74 mgKOH / g. A carboxylic acid-containing photosensitive resin (varnish A-1) having a solid content concentration of 65% was obtained.

Resin synthesis example 2 (A-2)
To 800 g of diethylene glycol monoethyl ether acetate, 442.2 parts (3.3 moles) of dimethylolpropionic acid, 1031.8 parts (6.7 moles) of methacrylic anhydride, 3.0 parts of methylhydroquinone, 8.5 parts of triphenylphosphine Part was added and reacted at 95 ° C. for 8 hours. Next, 1000 g of diethylene glycol monoethyl ether acetate, orthocresol novolak type epoxy resin [Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 2846.2 g (glycidyl) Base number (total number of aromatic rings): 13.3 mol), 442.2 parts (3.3 mol) of dimethylolpropionic acid, 3.0 parts of methylhydroquinone, and 1300 parts of carbitol acetate were heated to 90 ° C. with stirring. The reaction mixture was dissolved. Next, the reaction solution was cooled to 60 ° C., charged with 12.0 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 25 hours. Next, 1064 parts (7.0 mol) of tetrahydrophthalic anhydride was added thereto, heated to 95 ° C., reacted for about 6 hours, then cooled, and the acid value of the solid component was 67 mgKOH / g. A carboxylic acid-containing photosensitive resin (varnish A-2) having a solid content concentration of 65% was obtained.

Resin synthesis example 3 (A-3)
To 600 g of diethylene glycol monoethyl ether acetate, 670 parts (5.0 mol) of dimethylolpropionic acid, 1.5 parts of methylhydroquinone and 7.5 parts of triphenylphosphine were added and heated to 80 ° C. with stirring to dissolve. Into this, 770 parts (5.0 mol) of methacrylic anhydride dissolved in 750 g of diethylene glycol monoethyl ether acetate was gradually added dropwise over 2 hours, followed by reaction for 5 hours. Next, orthocresol novolak type epoxy resin [Dainippon Ink Chemical Co., Ltd., EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 2140 g (number of glycidyl groups (total number of aromatic rings): 10. 0 mol), 3.5 parts of methylhydroquinone and 1100 parts of carbitol acetate were added and heated to 90 ° C. with stirring to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 12.0 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 25 hours. Next, 1064 parts (7.0 mol) of tetrahydrophthalic anhydride was added thereto, heated to 95 ° C., reacted for about 6 hours, then cooled, and the acid value of the solid component was 85 mgKOH / g. A carboxylic acid-containing photosensitive resin (varnish A-3) having a solid content concentration of 65% was obtained.

Resin synthesis example 4 (A-4)
After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide in 400 parts of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C., 81.2 parts of 98.5% NaOH at 70 ° C. with stirring. Added over 100 minutes. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 10 parts of 30% NaOH was added at 70 ° C. The reaction was carried out for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was recovered from the oil layer by distillation to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ° C.

  Next, 600 g of diethylene glycol monoethyl ether acetate, 442.2 parts (3.3 mol) of dimethylolpropionic acid, 1031.8 parts (6.7 mol) of methacrylic anhydride, 3.0 parts of methylhydroquinone, triphenylphosphine 8 .5 parts was added and reacted at 95 ° C. for 8 hours. Next, 700 g of diethylene glycol monoethyl ether acetate, 2900 parts (10 mol) of epoxy resin (a-1), 3.0 parts of methylhydroquinone, and 1000 parts of carbitol acetate were added and heated to 90 ° C. and stirred to dissolve the reaction mixture. . Next, the reaction solution was cooled to 60 ° C., charged with 16.7 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours. Next, 786 parts (7.86 mol) of succinic anhydride and 450 parts of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, and after cooling, the acid value of the solid content was 85 mgKOH / g. A carboxylic acid-containing photosensitive resin (varnish A-4) having a solid content of 65% was obtained.

Resin synthesis example 5 (A-5)
700 g of diethylene glycol monoethyl ether acetate, 442.2 parts (3.3 moles) of dimethylolpropionic acid, 1031.8 parts (6.7 moles) of methacrylic anhydride, 3.0 parts of methylhydroquinone, 8.5 parts of triphenylphosphine Part was added and reacted at 95 ° C. for 8 hours. Next, 950 g of diethylene glycol monoethyl ether acetate, orthocresol novolac type epoxy resin [manufactured by Dainippon Ink and Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 2140 g (glycidyl group number ( Total number of aromatic rings): 10.0 mol), 3.0 parts of methylhydroquinone and 1000 parts of carbitol acetate were charged, heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., 10.0 parts of triphenylphosphine was charged, heated to 100 ° C., and reacted for about 30 hours. Next, 1140.0 parts (7.5 mol) of tetrahydrophthalic anhydride was added thereto, heated to 95 ° C., and reacted for about 6 hours. Further, 213.0 g (1.5 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was performed at 115 ° C. for 4 hours. The solid content acid value was 68 mgKOH / g, and the solid content concentration was 65%. An acid-containing photosensitive resin (varnish A-5) was obtained.

Comparative Synthesis Example 1 (R-1)
Orthocresol novolac type epoxy resin (Dainippon Ink & Chemicals, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups (fragrance) Total number of rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and heated and stirred at 100 ° C. to obtain a uniform solution. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction solution, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 4 hours. After cooling, the solid content acid value 89 mgKOH / G, a resin solution having a solid content of 65% was obtained. This is named Varnish R-1.

Comparative Synthesis Example 2 (R-2)
Orthocresol novolac type epoxy resin [Dainippon Ink Chemical Co., Ltd., EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6] 1070 g (diglycol group number (fragrance) Total number of rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and heated and stirred at 100 ° C. to obtain a uniform solution. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, and further 1.6 g of triphenylphosphine was added, and the temperature was raised to 120 ° C. and reacted for another 12 hours. To the obtained reaction solution, 525 g of aromatic hydrocarbon (Sorvesso 150) and 608 g (4.0 mol) of tetrahydrophthalic anhydride were charged and reacted at 110 ° C. for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylate was added to the obtained reaction solution and reacted at 115 ° C. for 4 hours to obtain a resin solution having a solid content acid value of 77 mgKOH / g and a solid content of 65%. This is named Varnish R-2.

Comparative Synthesis Example 3 (R-3)
After dissolving 925 parts of epichlorohydrin and 462.5 parts of dimethyl sulfoxide in 400 parts of bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C., 81.2 parts of 98.5% NaOH at 70 ° C. with stirring. Added over 100 minutes. After the addition, the reaction was further carried out at 70 ° C. for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone, and further 10 parts of 30% NaOH was added at 70 ° C. The reaction was carried out for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was recovered from the oil layer by distillation to obtain 370 parts of an epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 ° C. 2900 parts (10 equivalents) of epoxy resin (a-1), 720 parts (10 equivalents) of acrylic acid, 2.8 parts of methylhydroquinone, and 1950 parts of carbitol acetate are heated and stirred at 90 ° C. to dissolve the reaction mixture. did. Next, the reaction solution was cooled to 60 ° C., charged with 16.7 parts of triphenylphosphine, heated to 100 ° C., and reacted for about 32 hours to obtain a reaction product having an acid value of 1.0 mg KOH / g. Next, 786 parts (7.86 mol) of succinic anhydride and 423 parts of carbitol acetate were added to this, heated to 95 ° C., reacted for about 6 hours, solid content acid value 100 mg KOH / g, solid content 65% A resin solution was obtained. This is named Varnish R-3.

Example 1
Using the resin solution of the above synthesis example, various components shown in Table 1 were blended in respective proportions (parts by mass), premixed with a stirrer, and then kneaded with a three-roll mill to prepare a photocurable resin composition. did. Here, it was 15 micrometers or less when the dispersion degree of the obtained photocurable resin composition was evaluated by the particle size measurement by the grindometer by an Erichsen company.

Performance evaluation:
<Optimum exposure amount>
Each of the prepared photocurable resin compositions is applied to the entire surface of a circuit pattern substrate having a copper thickness of 35 μm after polishing with buffalo, washed with water, dried, and then screen-printed to circulate at 80 ° C. Dry in an oven for 30 minutes. After drying, direct drawing device (Parbot 8000 made by Orbotech) equipped with a semiconductor laser with a maximum wavelength of 355 nm, direct drawing exposure machine equipped with a high-pressure mercury lamp (direct drawing exposure machine equipped with an ultra-high pressure mercury lamp lamp, Marculex made by Dainippon Screen) or high pressure Exposure through a step tablet (Kodak No 2) using an exposure apparatus equipped with a mercury lamp (ORC Co., Ltd. mounted with a mercury short arc lamp), and development (30 ° C., 0.2 MPa, 1 mass% sodium carbonate aqueous solution) for 60 seconds The amount of exposure of the step tablet remaining at the time of 7 was determined as the optimum exposure amount when the pattern was 7 steps.

<Dry touch dryness>
Each of the prepared photocurable resin compositions is applied onto the patterned copper foil substrate by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. A negative film made of PET was applied to this substrate, and pressure-bonded under reduced pressure with ORC (HMW680-GW20) for 1 minute, and then the sticking state of the film when the negative film was peeled off was evaluated.

○: The film peels without resistance.

(Triangle | delta): Although a film peels, a trace is attached to the coating film.

X: There is resistance when the film is peeled off, and the coating film has a clear mark.

<Maximum development life>
Each prepared said photocurable resin composition is apply | coated whole surface by screen printing on the copper foil board | substrate with which pattern formation was carried out, and it dries at 80 degreeC. From 20 minutes to 80 minutes after the start of the drying, the substrate is taken out every 10 minutes and allowed to cool to room temperature. The substrate was developed with a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. under a spray pressure of 2 kg / cm ² for 60 seconds, and the maximum allowable drying time in which no residue remained was defined as the maximum development life.

Characteristic test:
(Preparation of coating film property evaluation board)
Each of the photocurable resin compositions is applied on the entire surface of a patterned copper foil substrate by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. This substrate is exposed to a solder resist pattern at an optimum exposure amount using a direct writing apparatus equipped with a semiconductor laser having a maximum wavelength of 355 nm, and a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. is applied under a spray pressure of 2 kg / cm ^2. Development was performed for 2 seconds to obtain a resist pattern. This substrate was irradiated with ultraviolet rays under a condition of an integrated exposure amount of 1000 mJ / cm ^{2 in} a UV conveyor furnace, and then cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.

○ ^* : No peeling is observed even after 10 seconds of immersion for 6 or more times.

○: No peeling is observed even if the immersion for 10 seconds is repeated 3 times or more.

(Triangle | delta): It peels for a while when immersion for 10 seconds is repeated 3 times or more.

X: The resist layer swells and peels off within 3 times for 10 seconds.

<Electroless gold plating resistance>
Using a commercially available electroless nickel plating bath and electroless gold plating bath, plating is performed under the conditions of nickel 0.5 μm and gold 0.03 μm, and the presence or absence of peeling of the resist layer or penetration of the plating is visually confirmed. After the evaluation, the presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.

○ ^* : No soaking or peeling is observed.

○: Slight penetration is confirmed after plating, but does not peel off after tape peeling.

Δ: Slight penetration after plating and peeling after tape peel.

X: There is peeling after plating.

<Alkali resistance>
The evaluation substrate was immersed in a 10 vol% NaOH aqueous solution at room temperature for 30 minutes, and the infiltration and dissolution of the coating film were visually confirmed. Further, peeling by tape beer was confirmed.

○: There is no penetration or dissolution, and no peeling is confirmed after the tape peel.

(Triangle | delta): There is no bleed-in and melt-out, and a slight peeling is recognized after a tape peel.

X: Permeation and dissolution, or peeling after tape peeling.

<PCT resistance>
The evaluation substrate was treated for 50 hours under the conditions of 121 ° C., saturation and 0.2 MPa using a PCT device (HEST SYSTEM TPC-412MD manufactured by ESPEC CORP.), And the state of the coating film was visually confirmed, and further the tape The peeling due to the peel was confirmed. Judgment criteria are as follows.

○: There is no penetration or dissolution, and no peeling is confirmed after the tape peel.

(Triangle | delta): There is no bleed-in and melt-out, and a slight peeling is recognized after a tape peel.

X: Permeation and dissolution, or peeling after tape peeling.

<PCBT resistance>
An evaluation board was produced under the above conditions using IPC B-25 comb-type electrode B coupon instead of the copper foil substrate, and a bias voltage of DC 30 V was applied to the comb-type electrode. System TPC-412MD) was used for 96 hours under the conditions of 121 ° C. and 97% humidity, and the presence or absence of discoloration or migration was evaluated. Judgment criteria are as follows.

○ ^* : No discoloration or migration.

○: Only slight discoloration or migration has occurred.

Δ: Discoloration or migration has occurred.

X: Discoloration is remarkable and migration reaches from one electrode to the other.

<Electrical characteristics>
An evaluation board was prepared under the above conditions using IPC B-25 comb electrode B coupon instead of copper foil substrate, a bias voltage of DC 100 V was applied to the comb electrode, and a constant temperature of 85 ° C. and humidity 85%. The presence or absence of migration after 1,000 hours was confirmed in a constant humidity bath. The judgment criteria are as follows.

○: No change is observed at all.

Δ: Slightly changed.

×: Migration has occurred.

<Color of coating film>
The color of the cured product was judged visually.

The results are shown in Table 2.

Example 2
<Dry film evaluation>
Composition Example 1 used in Example 1 was diluted with methyl ethyl ketone, applied onto a PET film, and dried at 80 ° C. for 30 minutes to form a photosensitive resin composition layer having a thickness of 20 μm. Further, a cover film was laminated thereon to obtain a dry film. Then, the cover film was peeled off, the film was heat-laminated on the patterned copper foil substrate, and then exposed under the same conditions as the substrate used for the coating film property evaluation of Example 1. After the exposure, the carrier film was peeled off, and heat-cured for 60 minutes with a hot air dryer at 150 ° C. to prepare a test substrate. About the test substrate which has the obtained cured film, the evaluation test of each characteristic was done with the test method and evaluation method which were mentioned above. The results are shown in Table 3.

  As can be seen from the results shown in Tables 2 and 3 in Examples 1 and 2, the photocurable resin composition containing the carboxylic acid-containing photosensitive resin (A) of the present invention is a conventional resin. In comparison, it has high sensitivity and is excellent in developability, dryness to touch, solder heat resistance, electroless gold plating resistance, alkali resistance, PCT resistance, and PCBT resistance, and is useful as a resist ink. In addition, the photocurable resin composition of the present invention can be applied with high sensitivity to monochromatic light such as i-line and h-line or laser light, and also to an ultraviolet light source such as a high-pressure mercury lamp. I understand.

Claims (8)

(A) a carboxylic acid-containing photosensitive resin having a structure represented by the general formula (I), (B) a photopolymerization initiator, and (C) a compound having two or more ethylenically unsaturated groups in one molecule. a luer alkaline developable photocurable resin composition to contain, by using an epoxy compound having at least two epoxy groups in one molecule (a) a carboxylic acid-containing photosensitive resin (c) A photocurable resin composition capable of being developed with an alkali and having a content of the carboxylic acid-containing photosensitive resin (A) of 20 to 60% by mass with respect to the total mass of the composition :

In general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms, and R ³ represents an acid anhydride residue. The (B) photopolymerization initiator is
An oxime ester photopolymerization initiator containing a structure represented by the following general formula (II):
1 selected from the group consisting of an aminoacetophenone photopolymerization initiator containing a structure represented by the following general formula (III) and an acylphosphine oxide photopolymerization initiator containing a structure represented by the following general formula (IV) The photocurable resin composition capable of alkali development according to claim 1, wherein the photocurable resin composition is a seed or a mixture of two or more kinds:

In General Formulas (II) to (IV), R ¹ is a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), or 1 to 20 carbon atoms. A linear, branched or cyclic alkyl group (which may be substituted with one or more hydroxyl groups, and may have one or more oxygen atoms in the middle of the alkyl chain), 5 to 5 carbon atoms An cycloalkyl group having 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ² is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (one Which may be substituted with the above hydroxyl groups and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or Represents a benzoyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group);
R ³ and R ⁴ each independently represents a linear, branched or cyclic alkyl group or arylalkyl group having 1 to 12 carbon atoms,
R ⁵ and R ⁶ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ⁵ and R ⁶ are bonded to form a cyclic alkyl ether group. You may,
R ⁷ and R ⁸ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group, a cyclohexyl group, a cyclopentyl group, an aryl group (halogen atom, alkyl group, or alkoxy group). Or an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms). However, the case where both R ⁷ and R ⁸ are R—C (═O) — groups is excluded.   The alkali-developable photocurable resin composition according to claim 1, further comprising (D) a thermosetting component.   Furthermore, (E) It is a soldering resist containing a coloring agent, The photocurable resin composition which can be alkali-developed as described in any one of Claims 1 thru | or 3 characterized by the above-mentioned.   The photocurable dry film obtained by apply | coating the photocurable resin composition as described in any one of Claims 1 thru | or 4 to a carrier film, and drying.   It is a hardened material pattern formed using the resin layer which consists of a photocurable resin composition as described in any one of Claims 1 thru | or 4, Comprising: Pattern formation was performed by active energy ray irradiation. Hardened product pattern.   A cured product pattern in which pattern formation by active energy ray irradiation according to claim 6 is performed by direct drawing using an active energy ray having a wavelength of 350 nm to 410 nm.   The printed wiring board which comprises the hardened | cured material pattern of Claim 6 or 7 on a copper layer.